Reaction of α-Na12(As2W15O 56) with FeII in 1 M NaCl solution followed by air oxidation yields αααα-H2Na 14[(NaOH2)2FeIII2-(As2W15O56)2] (Na2), the arsenic analogue of the divacant lacunary sandwich, ααα α-H2Na14[(NaOH2)2Fe III2(P2W15O56) 2] (Na1). This complex (Na2) consists of a Na2Fe 2 central unit sandwiched between two B-α-As2W 15O5612- moieties. Both Na1 and Na2 react with one equivalent of FeIII to give ααβα-Na 14[(NaOH2)(FeIIIOH2)(Fe III)2(X2W15O56) 2], where X = P (Na3) or As (Na4), or two equivalents of Mn II to give αββα-Na14[(Mn IIOH2)2(FeIII)2(X 2W15O56)2], where X = P (Na5) or As (Na6). A single-crystal X-ray diffraction analysis of Na5 has been carried out [a = 13.5387(8) Å, b = 13.9327(9) Å, c = 21.3347(13) Å, α = 92.921(1) °, β = 94,367(1) °, γ = 118.154(1) °, triclinic, P1̄, R1 = 5.49%, based on 24662 independent reflections], which revealed a Mn2Fe2 central unit sandwiched between two B-α-P2W15O5612- units. All of the new complexes have been characterized by FTIR spectroscopy, UV/Visible spectroscopy, elemental analyses, and cyclic voltammetry, and they are all stable for at least 24 h over a wide pH range (0-7), except for Na4, which is unstable below pH 2.
|Original language||English (US)|
|Number of pages||5|
|Journal||European Journal of Inorganic Chemistry|
|State||Published - Nov 7 2003|
- Sandwich complexes